The development of a detailed understanding of the influence of surface chemical structure on mammalian cell attachment has been confronted with difficulties. Not only are the biological problems inherently complex, but until recently there have not been adequately well defined model surfaces for fundamental studies. The advent of self-assembled monolayers (SAMs) has promised to transform this situation, by providing well-defined surfaces with structures and chemistries that may readily be controlled, and the past five years have seen growing interest in the use of SAMs to model cellular interactions with artificial substrata. In the present work, SAMs with a range of alkyl chain lengths and terminal groups have been used in studies of the attachment of murine 3T3 fibroblasts and primary human osteoblast-like cells. The sensitivity of cellular attachment to subtle changes in adsorbate molecular structure and order has been explored. The responses of cells to micropatterned substrata formed using photopatterning methods have been explored. The organisation of structural elements, including filamentous actin organisation and focal contact formation, within the cell cytoskeleton has been explored using immunochemical methods. The effect of protein adsorption has been probed by comparing attachment from serum-free and full media, and by pre-exposing surfaces to protein solutions. Valuable insights have been gathered into the relationship between surface chemical structure and cellular behaviour.